CN116650362A

CN116650362A - Composition comprising a UV screening agent, an acrylic copolymer and an acrylamidomethylpropane sulfonic acid copolymer

Info

Publication number: CN116650362A
Application number: CN202310600161.3A
Authority: CN
Inventors: C.吉拉芒; R.罗兰; S.特鲁安-克利; M-L.希龙; K.布特莱
Original assignee: LOreal SA
Current assignee: LOreal SA
Priority date: 2017-11-15
Filing date: 2018-11-15
Publication date: 2023-08-29
Also published as: RU2020116462A3; BR112020008448B1; RU2020116462A; US20200281829A1; FR3073405A1; FR3073405B1; JP2021502395A; RU2769315C2; JP7028971B2; CN111356503A; EP3710117A1; WO2019096961A1; BR112020008448A2

Abstract

The present application relates to a composition, in particular a cosmetic composition, in particular a photoprotective composition, comprising at least: -one or more hydroxyethyl acrylate polymers, -one or more UV screening agents, and-one or more copolymers of acrylamido-2-methylpropanesulfonic acid with one or more nonionic monomers.

Description

Composition comprising a UV screening agent, an acrylic copolymer and an acrylamidomethylpropane sulfonic acid copolymer

The application is a divisional application with the application number of 201880073231.1, and the application date of the application with the application number of 201880073231.1 is 2018, 11, 15.

The present application relates to a composition, in particular a cosmetic composition, and in particular a photoprotective composition, and a method for treating keratin materials, in particular the skin and the skin crust, using said composition.

It is known that optical radiation having a wavelength between 280 and 400nm enables the human epidermis to be brown. However, light having a wavelength more particularly between 280 and 320nm (known as UVB light) causes skin erythema and sunburn, which can be detrimental to the development of natural tanning.

For these reasons, and also for aesthetic reasons, there is a constant need for means for controlling such natural tanning in order to control the colour of the skin; such UVB radiation should therefore be shielded.

It is also known that UVA light having a wavelength between 320 and 400 hill and causing the skin to turn brown is prone to cause adverse changes therein, especially in the case of sensitive skin or skin continuously exposed to solar radiation. UVA light causes in particular loss of skin elasticity and wrinkling, leading to premature skin aging.

It is therefore also desirable to shield UVA radiation.

A number of photoprotective compositions have been proposed to date for protecting against the effects caused by UVA and/or UVB light. These compositions generally contain organic or mineral masking agents, more particularly mixtures of organic liposoluble masking agents and/or water-soluble masking agents in combination with metal oxide pigments such as titanium dioxide or zinc oxide. These inorganic particles enable an increase in sun protection, which reduces the amount of organic masking agent and thus improves the cosmetic properties of the formulation.

Organic masking agents may lead to reduced organoleptic properties, in particular being greasy, sticky and/or shinier (green).

Stable compositions are sought that have high SPF without compromising cosmetic properties such as greasy appearance, tackiness and shine.

The inventors have unexpectedly found that a composition comprising a UV screening agent, a specific lipophilic polymer and a specific acrylamide-2-propanesulfonic acid copolymer enables to obtain a stable composition with high SPF and improved cosmetic properties. In particular, after application to the skin, there is no lightening effect and the skin is neither greasy nor tacky.

The present invention makes it possible to obtain compositions in various forms of presentation (for example creams or emulsions) which are stable over time and with respect to temperature and are organoleptically acceptable.

Compositions are considered stable when they exhibit little or no change in macroscopic and microscopic appearance, viscosity, and pH.

The present invention relates to a composition, in particular a cosmetic composition, in particular a photoprotective composition, comprising at least:

one or more copolymers described below,

-one or more UV screening agents, and

one or more copolymers of acrylamido-2-methylpropanesulfonic acid with one or more nonionic monomers.

According to the invention, the composition preferably comprises a physiologically acceptable medium.

According to another of its aspects, the present invention relates to a photoprotective cosmetic composition comprising, in a physiologically acceptable medium, a composition according to the invention as defined above.

The photoprotective cosmetic composition according to the invention is particularly suitable for carrying out a non-therapeutic method for photoprotection of keratin materials.

The photoprotective cosmetic compositions according to the present invention have an SPF of, for example, at least 5, or even at least 10, still better 15, still better at least 30, 45 or 60. SPF (solar protection factor) is defined in article A new substrate to measure sunscreen protection factors throughout the ultraviolet spectrum [ novel substrates measuring solar protection factors in the ultraviolet spectrum ], J.Soc.cosmetic.chem. [ society of cosmetic chemists ],40, 127-133 (June/June 1989)).

It is known practice to introduce into cosmetic compositions various active agents intended to provide specific treatments to the skin and/or hair. However, some of these active agents have the disadvantage of being chemically unstable and/or unstable to light. Thus, they lose their activity rapidly over time, and this instability is contrary to the desired efficacy. Particularly interesting active agents are in particular resveratrol, retinol, baicalin and vitamin C.

These active agents are very sensitive to certain environmental parameters such as light, oxygen and water. When these formulated active agents are contacted with one of these parameters in particular, their rapid degradation therefore occurs. Nowadays, due to the many beneficial properties of the active agents to the skin and/or hair, it has long been sought to formulate the active agents in various forms of presentation in the cosmetic and dermatological fields.

Thus, there remains a need for compositions, and in particular emulsions, containing photosensitive and/or oxidation-sensitive hydrophilic active agents, and in particular resveratrol, which are stable and have good cosmetic properties and which are compatible with the constraints of industrial implementation of the manufacturing process thereof.

The inventors have unexpectedly found that the use of a combination of a UV screening agent, a specific lipophilic polymer and a specific acrylamide-2-propanesulfonic acid copolymer in a composition comprising an oxidation-sensitive hydrophilic active agent enables to improve the stability and thus the efficacy of this active agent and to stabilize the composition comprising this active agent.

The bioavailability of these active agents is then improved after application to the skin.

Thus, the stable composition according to the invention is a composition which shows little or no change in macroscopic appearance (phase separation, change in color, etc.) or in microscopic appearance (recrystallisation of the active agent) after storage for 2, 4, 8 or 12 weeks at temperatures of 25 ℃, 4 ℃ and 40 ℃ and wherein the content of active ingredient remains stable at room temperature and after at least one month at 40 ℃.

According to a particular mode, the present invention relates to a composition, in particular a cosmetic composition, in particular a photoprotective composition, comprising at least:

a polymer of the type described below,

-one or more UV screening agents, and

one or more copolymers of acrylamido-2-methylpropanesulfonic acid with one or more nonionic monomers, and

-one or more photoactive agents.

According to another of its aspects, the present invention relates to a non-therapeutic method for photoprotecting keratin materials against solar UV radiation, comprising the step of applying the cosmetic composition according to the present invention to the keratin materials.

The invention also relates to a method for dyeing and/or lightening keratin materials, and to a method for modifying the spectral reflectance of keratin materials, each of these methods comprising the step of applying to the keratin materials a cosmetic composition according to the invention.

The invention also relates to a non-therapeutic cosmetic method for limiting skin darkening and/or improving the colour and/or uniformity of skin tone, said method comprising the step of applying to the skin a cosmetic composition according to the invention.

The invention also relates to a non-therapeutic cosmetic method for preventing and/or treating the signs of ageing of keratin materials, comprising the step of applying the cosmetic composition according to the invention to the surface of the keratin materials.

In the following and unless otherwise indicated, the limits of the ranges of values are included in the ranges, especially in the expressions "between.

The terms "AMPS" and "acrylamido-2-methylpropanesulfonic acid" are equivalently used in this patent application.

Furthermore, the expression "one or more" and "greater than or equal to" as used in the present specification is equivalent to the expression "at least one" and "at least", respectively.

Polymer a)

The composition according to the invention comprises at least one polymer a) comprising monomer units of formulae (a) and (B):

wherein:

r1 is independently selected in each instance from alkyl and alkenyl (alkenyl radial), and

At least 60% by weight of the radicals R1 being behenyl radicals, the weight percentages being relative to the sum of all the radicals R1 present in the polymer,

and is also provided with

The weight ratio of the sum of all hydroxyethyl acrylate units to the sum of all acrylate units carrying the radical R1 ranges from 1:30 to 1:1,

and the sum of the total units a and B is at least 95% by weight relative to the total weight of the polymer.

Preferably, R1 is constituted by an alkyl group, preferably a C16-C22 alkyl group, and more preferably a behenyl group (C22).

Preferably, at least 70% by weight, preferably at least 80% by weight, more preferably at least 90% by weight of the radicals R1 are behenyl radicals.

According to a preferred embodiment, all the radicals R1 are behenyl radicals.

Preferably, the weight ratio ranges from 1:15 to 1:1, and preferably ranges from 1:10 to 1:4.

Advantageously, the polymer units present in the polymer are constituted by the units (A) and (B) described previously.

The polymer has a number average molecular weight Mn ranging from 2000 to 9000g/mol, preferably ranging from 5000 to 9000 g/mol. The number average molecular weight may be measured via gel permeation chromatography, for example, according to the methods described in the examples below.

Preferably, the polymer has a melting point ranging from 60 ℃ to 69 ℃, and preferably ranging from 63 ℃ to 67 ℃. Melting points are measured by Differential Scanning Calorimetry (DSC), for example, according to the method described in the examples below.

The polymers used according to the invention can be prepared by polymerizing monomers of the formula ch2=ch-COO-R1 (R1 having the meaning described previously) with 2-hydroxyethyl acrylate.

The polymerization may be carried out according to known methods, such as solution polymerization or emulsion polymerization.

Polymerization is described, for example, in US 2007/0264204.

The lipophilic polymer according to the invention is present in the composition in a concentration ranging from 0.1% to 10%, even more preferably from 0.2% to 8% by weight, and even more particularly from 0.5% to 5% by weight.

AMPS copolymers

The composition according to the invention comprises at least one copolymer of acrylamido-2-methylpropanesulfonic acid or salts thereof with one or more nonionic monomers.

According to the inventionThe copolymer may be crosslinked or uncrosslinked.

When the polymer is crosslinked, the crosslinking agent may be selected from polyethylenically unsaturated compounds that are commonly used to crosslink polymers obtained by free radical polymerization.

Examples of crosslinking agents that may be mentioned include divinylbenzene, diallyl ether, dipropylene glycol diallyl ether, polyethylene glycol diallyl ether, triethylene glycol divinyl ether, hydroquinone diallyl ether, ethylene glycol or tetraethylene glycol di (meth) acrylate, trimethylolpropane triacrylate, methylenebisacrylamide, triallylamine, triallylmethacrylate, diallyl maleate, tetraallylethylene diamine, tetraallyloxyethane, trimethylol propane diallyl ether, allyl (meth) acrylate, allyl ethers of alcohols of the sugar series, or allyl or vinyl ethers of other polyfunctional alcohols, and also allyl esters of phosphoric acid and/or vinylphosphonic acid derivatives, or mixtures of these compounds.

According to a preferred embodiment of the invention, the crosslinking agent is selected from the group consisting of methylenebisacrylamide, allyl methacrylate and trimethylolpropane triacrylate (TMPTA). The degree of crosslinking generally ranges from 0.01mol% to 10mol% and more particularly from 0.2mol% to 2mol% relative to the polymer.

The copolymer according to the invention is composed ofAnd from one or more hydrophilic or hydrophobic ethylenically unsaturated nonionic monomers and, if they are crosslinked, one or more crosslinking agents (such as those defined above). When the copolymer includes hydrophobic ethylenically unsaturated monomers, these monomers may include one or more fatty chains.

For the purposes of the present invention, the term "fatty chain" means any hydrocarbon-based chain comprising at least 7 carbon atoms.

The 2-acrylamido-2-methylpropanesulfonic acid monomer of the copolymer contained in the composition according to the invention is in free form or is partially or completely neutralized by: mineral bases (sodium hydroxide, potassium hydroxide or ammonia) or organic bases (such as mono-, di-or triethanolamine, aminomethyl propanediol, N-methylglucamine), basic amino acids (such as arginine and lysine), and also mixtures of these compounds.

Preferably, the 2-acrylamido-2-methylpropanesulfonic acid monomer according to the invention is partially or completely salified in the form of ammonium or sodium salts.

Preferably, the 2-acrylamido-2-methylpropanesulfonic acid monomer according to the invention is completely salified, preferably in the form of ammonium or sodium salts.

According to the inventionThe copolymer contains one or more nonionic monomers selected from the group consisting of water-soluble ethylenically unsaturated monomers, hydrophobic monomers, and mixtures thereof.

Among the nonionic water-soluble monomers, examples that may be mentioned include:

a (meth) acrylamide which is a compound of formula (I),

n-vinylacetamide and N-methyl-N-vinylacetamide,

N-vinylformamide and N-methyl-N-vinylformamide,

-maleic anhydride and the like,

the reaction of the vinyl amine with the catalyst,

n-vinyllactams comprising cycloalkyl groups having from 4 to 9 carbon atoms, such as N-vinylpyrrolidone, N-butyrolactam and N-vinylcaprolactam,

-CH ₂ Vinyl alcohol of the type CHOH,

-a water-soluble vinyl monomer of formula (B):

wherein:

-R ₁₅ selected from H, -CH ₃ 、-C ₂ H ₅ and-C ₃ H ₇ ；

-X ₂ Selected from:

--OR ₁₆ alkyl oxides of the type wherein R ₁₆ Is an aromatic hydrocarbon containing from 1 to 6 carbon atoms, optionally substituted with halogen (iodine, bromine, chlorine or fluorine) atoms; hydroxyl (-OH); ether substituted straight or branched chain, saturated or unsaturated hydrocarbon-based groups.

For example, glycidyl (meth) acrylate, hydroxyethyl (meth) acrylate, and (meth) acrylic esters of ethylene glycol, diethylene glycol or polyalkylene glycol are mentioned.

Preferably, the water-soluble monomer is selected from the group consisting of acrylamide, vinylpyrrolidone and hydroxyalkyl (meth) acrylate, more particularly vinylpyrrolidone.

As according to the inventionCopolymers with hydrophilic monomers, examples which may be mentioned include:

copolymers of acrylamido-2-methylpropanesulfonic acid with vinylpyrrolidone, in particular the commercial product Aristoflex AVC, sold by the company Clariant,

Crosslinked acrylamide/acrylamido-2-methylpropanesulfonic acid sodium copolymer, as used in commercial products Sepigel(INCI name: polyacrylamide/C ₁₃ -C ₁₄ Copolymers in isoparaffin/laureth-7), or in the use under the name Simulgel by Sibirk Co (SEPPIC)>(INCU name: acrylamide/sodium acryloyldimethyl taurate copolymer/isohexadecane/polysorbate-/d.>) In commercial products for sale;

-with hydroxy ethyl acrylateCopolymers, e.g.)>Sodium/hydroxyethyl acrylate copolymer, as used in commercial products sold under the name Simulgel NS (CTFA name: hydroxyethyl acrylate/sodium acryloyldimethyl taurate copolymer (and) squalane (and) polysorbate 60) by Sibirk company.

Among the hydrophobic monomers that may be mentioned are examples including:

styrene and its derivatives, such as 4-butylstyrene, alpha-methylstyrene and vinyltoluene;

-CH ₂ ＝CH-OCOCH ₃ Vinyl acetate of (a);

-CH ₂ Vinyl ether of CHOR, wherein R is a linear or branched, saturated or unsaturated hydrocarbon-based group containing from 1 to 20 and preferably from 1 to 6 carbon atoms;

-acrylonitrile;

-caprolactone;

vinyl chloride and vinylidene chloride;

-a hydrophobic vinyl monomer of formula (C):

wherein:

-R ₂₃ selected from H, -CH ₃ 、-C ₂ H ₅ and-C ₃ H ₇ Preferably, the reaction mixture is H,

-X ₃ selected from:

--OR ₂₄ alkyl oxides of the type wherein R ₂₄ Is a linear or branched, saturated or unsaturated hydrocarbon-based group containing from 1 to 6 carbon atoms. The hydrocarbon-based group is preferably an alkyl or alkenyl group. For example, methyl methacrylate, ethyl methacrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl acrylate, isobornyl acrylate and 2-ethylhexyl acrylate are mentioned;

-a vinyl monomer of formula (D):

wherein R is ₁ C representing a hydrogen atom or a straight or branched chain ₁ -C ₆ Alkyl, preferably methyl; y represents O or NH; r is R ₂ Represents a hydrophobic hydrocarbon-based group comprising from 8 to 50 carbon atoms, more preferably from 8 to 22 carbon atoms, and even more preferably from 10 to 18 carbon atoms; x represents a number ranging from 0 to 100.

According to a specific embodiment of the invention, in formula (D), Y represents an oxygen atom.

According to a particular embodiment of the invention, in formula (D), the radical R ₁ Represents methyl.

According to a particular embodiment of the invention, x represents an integer ranging from 3 to 40, and preferably from 5 to 30.

The hydrocarbon-based group is preferably an alkyl or alkenyl group, and more particularly an alkyl group.

The monomers of formula D are preferably selected from C (meth) acrylic acids comprising from 5 to 40 oxyethylene groups ₈ -C ₂₂ Alkyl esters.

Copolymers of AMPS with monomers of formula (D) are described in particular in patent application FR 2 818 540. The paragraphs in said patent application that specifically describe these polymers have been incorporated into the present patent application.

More particularly, the hydrophobic monomer is selected from the monomers of formula (D).

Copolymers of AMPS with hydrophobic monomers are, for example, AMPS/cetostearyl methacrylate copolymers ethoxylated with 25mol of ethylene oxide (80/20), which are crosslinked with trimethylolpropane triacrylate (TMPTA), in particular sold by the company Clariant under the name Aristoflex HMS (INCI name: ammonium acryloyldimethyl taurate/steareth-25 methacrylate crosslinked polymer); and AMPS/Behenyl methacrylate copolymer ethoxylated with 25mol of ethylene oxide, crosslinked with trimethylolpropane triacrylate (TMPTA), under the name of Kernen CorpHMB (INCI name: ammonium acryloyldimethyl taurate/behenate polyether-25 methacrylate cross-linked polymer) is sold.

As copolymers of AMPS with nonionic hydrophobic monomers, mention may also be made of non-crosslinked copolymers of AMPS with lauryl methacrylate ethoxylated with 7mol of ethylene oxide, such as LNC (INCI name: ammonium acryloyldimethyl taurate/laureth-7 methacrylate copolymer) or non-crosslinked copolymers of AMPS with stearyl methacrylate ethoxylated with 8mol of ethylene oxide, e.g. & lt & gt>SNC (INCI name: ammonium acryloyldimethyl taurate/steareth-8 methacrylate copolymer).

The invention is characterized in thatThe copolymer preferably has a molar mass ranging from 20 to 10 000g/mol, preferably from 80 to 8 000g/mol, and even more preferably from 100 to 7 000 g/mol.

As according to the inventionCopolymers may be mentioned more particularly:

copolymers of acrylamido-2-methylpropanesulfonic acid ammonium with vinylpyrrolidone, such as the commercial product Aristoflex AVC sold by the company Craien,

AMPS/cetostearyl methacrylate ethoxylated with 25mol of ethylene oxide, crosslinked with trimethylolpropane triacrylate (TMPTA), sold by the company Craien under the name Aristoflex HMS.

According to a more preferred variant of the invention, the copolymer of AMPS with nonionic monomers according to the invention is a copolymer of acrylamide-2-methylpropanesulfonic acid ammonium with vinylpyrrolidone.

The AMPS copolymer according to the present invention may be present in the composition according to the present invention in an amount ranging from 0.1% to 10% relative to the total weight of the composition, preferably from 0.2% to 5% by weight, and more preferably from 0.5% to 4% by weight.

UV screening agent

The composition according to the invention further comprises at least one UV-screening agent (agent for screening off UV radiation from sunlight). The UV screening agent may be selected from hydrophilic, lipophilic or insoluble organic and inorganic UV screening agents, and mixtures thereof.

The term "UV screening agent" means a substance capable of absorbing at least a portion of UV radiation emitted by the sun to protect the skin and/or lips and/or hair from the deleterious effects of such radiation.

The UV screening agent is a UV screening agent commonly used in cosmetics. It may be selected from the positive list contained in annex VI of code 1223/2009 (EC), which specifies a list of UV screening agents allowed in cosmetics.

According to a specific embodiment, the UV screening agent is present in the composition according to the invention in an active material content ranging from 0.1% to 60% by weight, and in particular from 5% to 45% by weight, relative to the total weight of the composition.

The water-soluble organic UV-screening agent is selected in particular from the following families:

water-soluble screening agent capable of absorbing UV light (UVA) from 320 to 400nm

Terephthalylene dicamphsylic acid (Terephthalylidenedicamphorsulfonic acid), manufactured by Chimex under the name Mexoryl SX,

bis-benzoxazolyl derivatives, as described in EP 669 323 and US 2 463 264, and more particularly the compound disodium phenylbisbenzimidazole tetrasulphonate, are sold under the trade name Neo Heliopan AP by haman and ramier company (Haarmann & Reimer).

The preferred masking agent is terephthal-methylenedicarbamate sulfonic acid.

Water-soluble screening agent capable of absorbing UV light (UVB) from 280 to 320nm

Para aminobenzoic acid (PABA) derivatives

PABA，

Glyceryl PABA

PEG-25PABA, sold by Basf under the name Uvinul P25,

phenylbenzimidazole sulfonic acid, particularly sold under the trade name Eusolex232 by Merck,

ferulic acid is used for preparing the medicine,

salicylic acid is used as a surfactant in the preparation of a pharmaceutical composition,

DEA methoxy cinnamic acid ester,

benzylidene camphorsulfonic acid, manufactured by the company chismann under the name Mexoryl SL,

camphorbenzalkonium methyl sulfate, manufactured by chimneman corporation under the name Mexoryl SO.

The preferred masking agent is phenylbenzimidazole sulfonic acid.

Mixed UVA and UVB water soluble screening agents

Benzophenone derivatives comprising at least one sulfonic acid group

Benzophenone-4, sold under the trade name Uvinul MS40 by Basoff company,

benzophenone-5, and

benzophenone-9.

When the absorber is an organic UV screening agent of the sulphonic acid type, it is preferably combined with an amount of an organic base such as an alkanolamine to render it water soluble.

The term "alkanolamine" means a C comprising at least one primary, secondary or tertiary amine functionality and at least one alcohol, typically a primary alcohol functionality ₂ -C ₁₀ A compound.

As suitable alkanolamines, tromethamine (tromethamine) and triethanolamine may be mentioned.

Organic masking agents that are hydrophobic or insoluble in common solvents may be selected, inter alia, from different families of compounds.

Hydrophobic screening agent capable of absorbing UV light (UVA) from 320 to 400nm

Dibenzoylmethane derivatives

Butyl methoxydibenzoylmethane, in particular sold under the trade name Parsol 1789 by Dissman nutrition products company (DSM Nutritional Products, inc.),

isopropyl dibenzoylmethane.

Aminobenzophenones

N-hexyl 2- (4-diethylamino-2-hydroxybenzoyl) benzoate sold by basf under the trade name Uvinul a+.

Anthranilic acid derivatives

Menthyl anthranilate, sold under the trade name Neo Heliopan MA by dexin corporation (Symrise).

4, 4-diaryl butadiene derivatives

1, 1-dicarboxy (2, 2' -dimethylpropyl) -4, 4-diphenylbutadiene.

Preferred masking agents are butyl methoxydibenzoylmethane and n-hexyl 2- (4-diethylamino-2-hydroxybenzoyl) benzoate.

Hydrophobic screening agent capable of absorbing UV light (UVB) from 280 to 320nm

Para aminobenzoate

An ethyl group, PABA, was used,

ethyl dihydroxypropyl group, PABA, was used,

ethylhexyl dimethyl PABA (Escalol 507 from ISP company).

Salicylic acid derivatives

Tricyclohexyl salicylate, sold under the name Eusolex HMS by Rona/EM Industries,

ethylhexyl salicylate, sold by Dexin under the name Neo Heliopan OS,

dipropylene glycol salicylate, sold by Scher under the name Dipsal,

TEA salicylate, sold by dexin company under the name Neo Heliopan TS.

Cinnamic acid esters

Ethylhexyl methoxycinnamate, in particular sold under the trade name Parsol MCX by Dissman nutrition products company,

isopropyl methoxycinnamate is used for preparing the high-purity sodium hydrogen carbonate,

isoamyl methoxycinnamate, sold under the trade name Neo Heliopan E1000 by dexin company,

Diisopropyl methyl cinnamate is used for preparing the medicine,

the composition of the cinnabar ester,

glyceryl ethyl hexanoate dimethoxy cinnamate.

Beta, beta' -diphenylacrylate derivatives

Octyl cyanobiphenyl acrylate, in particular sold by the company basf under the trade name Uvinul N539,

ethyl cyanobiphenyl acrylate, in particular sold by basf under the trade name Uvinul N35.

Benzylidene camphor derivatives

3-benzylidenecamphor, manufactured by the company Namexoryl SD,

methyl benzylidene camphor, sold by merck under the name Eusolex 6300,

polyacrylamidomethylbenzylidene camphor, manufactured by the company Chlamys under the name Mexoryl SW.

Triazine derivatives

Ethylhexyl triazone, in particular sold by the company basf under the trade name Uvinul T150,

diethyl hexyl butyramidotriazinone, sold under the trade name Uvasorb HEB by Sigma 3V company (Sigma 3V),

2,4, 6-tris (4' -aminobenzylidene-malonic acid dineopentyl) -s-triazine,

2,4, 6-tris (4' -aminobenzylidene-malonic acid diisobutyl) -s-triazine,

2, 4-bis (4 '-aminobenzylidene malonic acid dipivalyl ester) -6- (4' -aminobenzoic acid n-butyl ester) -s-triazine,

2, 4-bis (4' -aminobenzoic acid n-butyl) -6- (aminopropyl trisiloxane) -s-triazine,

Symmetrical triazine masking agents are described in patent US 6,225,467, patent application WO 2004/085 412 (see compounds 6 and 9) or U.S. new york, west henry theta (West henry tta, NY, USA) ip.com company ip.publication for document "Symmetrical Triazine Derivatives [ symmetrical triazine derivatives ]" (day 20 of 9 months 2004), especially 2,4, 6-tris (biphenyl) -1,3, 5-triazine (especially 2,4, 6-tris (biphenyl-4-yl-1, 3, 5-triazine)), and 2,4, 6-tris (terphenyl) -1,3, 5-triazine) also mentioned in bayer doff company (Beiersdorf) patent applications WO 06/035000, WO 06/034982, WO 06/034991, WO 06/035007, WO 2006/034992, WO 2006/034985.

Mention may also be made of 5,6,5',6' -tetraphenyl-3, 3' - (1, 4-phenylene) bis [1,2, 4-triazine ] (phenylene bis-diphenyltriazine).

Imidazoline derivatives

Dimethoxybenzylidene dioxoimidazoline propionic acid ethylhexyl ester.

Benzalmalonate derivatives

Polyorganosiloxanes containing benzalmalonate functions, such as, for example, silicone-15, sold by Dissman nutrition products company under the trade name Parsol SLX,

4' -methoxybenzylidene malonic acid dipivaloyl ester.

Merocyanine derivatives

Octyl 5-N, N-diethylamino-2-phenylsulfonyl-2, 4-pentadienoate.

Preferred masking agents are trimethylcyclohexyl salicylate, ethylhexyl salicylate, octyl cyanobiphenyl acrylate, ethylhexyl, methoxy cinnamate, isopentyl methoxy cinnamate, ethylhexyl triazone, and diethylhexyl butyryl triazone.

Most preferred are ethylhexyl salicylate, octyl cyanobiphenyl acrylate, ethylhexyl triazone, and ethylhexyl methoxycinnamate.

Is capable of absorbing UVA and UVB lightMixed hydrophobic masking agents for both threads

Benzophenone derivatives

Benzophenone-1, sold under the trade name Uvinul 400 by Basv company,

benzophenone-2, sold under the trade name Uvinul D50 by the company Basv,

benzophenone-3 or oxybenzone, sold by the company Basv under the trade name Uvinul M40,

benzophenone-5 is used as a base for the preparation of a pharmaceutical composition,

benzophenone-6, sold under the trade name Heliscorb 11 by Norquory,

benzophenone-8, sold under the trade name Spectra-Sorb UV-24 by the American cyanamide company (American Cyanamid),

benzophenone-10 is used as a base material for the preparation of a pharmaceutical composition,

benzophenone-11 is used as a base for the preparation of a pharmaceutical composition,

benzophenone-12.

Phenyl benzotriazole derivatives

Cresol trisiloxane, a solid form sold under the trade name MIXXIM BB/100 by the company Rhodia Chimie under the name Silatrizole, methylenebis (benzotriazole) tetramethylbutylphenol, by the company Phillips Nat chemical (Fairmount Chemical), or a micronized form sold under the trade name Tinosorb M by the company Ciba refinements (Ciba Specialty Chemicals).

Bis-resorcinol triazine derivatives:

bis (ethylhexyloxyphenol) methoxyphenyl triazine, sold under the trade name Tinosorb S by Ciba Geigy.

Benzoxazole derivatives

2, 4-bis [5-1 (dimethylpropyl) benzooxazol-2-yl- (4-phenyl) imino ] -6- (2-ethylhexyl) imino-1, 3, 5-triazine, sold by sigma 3V under the name uvassorb K2A.

Preferred masking agents are:

the composition of the cresol-trazotrisiloxane,

methylene bis-benzotriazolyl tetramethylbutylphenol,

bis (ethylhexyloxyphenol) methoxyphenyl triazine, and

benzophenone-3 or oxybenzone.

The most preferred masking agents are:

cresol trazotrisiloxane, and

bis (ethylhexyloxyphenol) methoxyphenyl triazine.

Also possible are screening agents of the merocyanine type having the formula and also the E/E-or E/Z-geometric isomeric forms thereof:

Wherein:

r is C ₁ -C ₂₂ Alkyl, C ₂ -C ₂₂ Alkenyl, C ₂ -C ₂₂ Alkynyl, C ₃ -C ₂₂ Cycloalkyl or C ₃ -C ₂₂ Cycloalkenyl, which may be interrupted by one or more O.

The above cyanine-type masking agents can be prepared according to the protocols described in WO 2007/071582, ip.com (2009), 9 (5A), 29-30IPCOM000182396D entitled "Process for producing-amino-2-cyclohexan-1-ylidene compounds [ method for producing 3-amino-2-cyclohexane-1-subunit compounds ] and US 4 749 643 (column 13, line 66-column 14, line 57 and references cited in this respect).

The organic masking agent may be present in the composition according to the invention in a concentration of between 0.1% and 50% by weight and preferably between 1% and 30% by weight relative to the total weight of the composition.

Inorganic sunscreens or photoprotective agents

The inorganic photoprotectant is selected from the group consisting of coated or uncoated metal oxide pigments (the average size of the primary particles is typically between 5nm and 100nm, preferably between 10nm and 50 nm), such as titanium oxide (amorphous or crystalline in rutile and/or anatase form), iron oxide, zinc oxide, zirconium oxide or cerium oxide pigments, all of which are UV photoprotectants known per se.

The pigment may or may not be coated.

The coated pigments are pigments which have been surface-treated with one or more of the chemical, electronic, mechanochemical and/or mechanical properties with a variety of compounds such as, for example, those described in Cosmetics & Toiletries, volume 105, pages 53-64, such as amino acids, beeswax, fatty acids, fatty alcohols, anionic surfactants, lecithins, sodium, potassium, zinc, iron or aluminum salts of fatty acids, metal (titanium or aluminum) alkoxides, polyethylene, silicones, proteins (collagen, elastin), alkanolamines, silicon oxides, metal oxides or sodium hexametaphosphate.

As is known, silicones are organosilicon polymers or oligomers of variable molecular weight comprising linear or cyclic and branched or crosslinked structures, obtained by polymerization and/or polycondensation of appropriately functionalized silanes and consisting essentially of a repetition of main units in which the silicon atoms are linked to each other via oxygen atoms (siloxane bonds), with optionally substituted hydrocarbon-based groups being directly linked to said silicon atoms via carbon atoms.

The term "silicone" also covers silanes, in particular alkylsilanes, which are required for its preparation.

The silicones suitable for coating pigments according to the invention are preferably selected from the group comprising: alkylsilanes, polydialkylsiloxanes and polyalkylhydrosiloxanes. Even more preferably, the silicone is selected from the group comprising: octyl trimethyl silane, polydimethylsiloxane and polymethylhydrosiloxane.

Needless to say, the metal oxide pigments may have been treated with other surface agents, in particular cerium oxide, aluminum oxide, silicon dioxide, aluminum compounds or silicon compounds, or mixtures thereof, before they are treated with silicone.

The coated pigments are more particularly titanium oxides which have been coated with:

silica, such as Sunveil from pool Tian Gongsi (Ikeda),

silicon dioxide and iron oxides, such as Sunveil F from Pond,

silica and alumina, such as products Microtitanium Dioxide MT 500 SA and Microtitanium Dioxide MT 100 SA from Imperial chemical company (Tayca) and Tiovil from titanium dioxide company (Tioxide),

alumina, such as the products Tipaque TTO-55 (B) and Tipaque TTO-55 (A) from Shi Yuan (Ishihara), and UVT 14/4 from Kemira,

Aluminum oxide and aluminum stearate, such as products Microtitanium Dioxide MT 100T, MT TX, MT 100Z and MT-01 from Imperial chemical company, products Solaveil CT-10W and Solaveil CT 100 from Li Kaima (Uniqema), and products Eusolex T-AVO from merck company,

silica, alumina and alginic acid, such as the products MT-100AQ from Imperial chemical company,

aluminum oxide and aluminum laurate, such as Microtitanium DioXide MT S from Imperial chemical company,

iron oxide and iron stearate, such as products Microtitanium Dioxide MT F from Imperial chemical company,

zinc oxide and zinc stearate, such as the products BR 351 from imperial chemical company,

silica and alumina and treated with silicones, such as products Microtitanium Dioxide MT SAS, microtitanium Dioxide MT 500 SAS or Microtitanium Dioxide MT 100 SAS from imperial chemical company,

silicon dioxide, aluminum oxide and aluminum stearate and treated with silicone, such as the product STT-30-DS from titanium industries, inc. (Titan Kogyo),

silica and treated with silicone, such as the product UV-Titan X195 from kami company,

alumina and treated with silicone, such as the product Tipaque TTO-55 (S) from the lithopone company, or UV Titan M262 from the kami la company,

Triethanolamine, such as the product STT-65-S from titanium industry Co., ltd,

stearic acid, such as Tipaque TTO-55 (C) from Shiyuan,

sodium hexametaphosphate, such as product Microtitanium Dioxide MT W from imperial chemical company;

TiO treated with octyl trimethylsilane ₂ Sold under the trade name T805 by Degussa silica company (Degussa silicones);

-TiO treated with polydimethylsiloxane ₂ Sold under the trade name 70250 Cardre UF TiO2SI3 by the company kokudo (Cardre); and

anatase/rutile TiO treated with polydimethyl hydrosiloxane ₂ Sold under the trade name Microtitanium Dioxide USP Grade Hydrophobic by Color technologies.

Uncoated titanium oxide pigments are sold, for example, by Imperial chemical company under the trade names Microtitanium Dioxide MT B or Microtitanium Dioxide MT B, by Degussa under the name P25, by Wackher under the name Transparent titanium oxide PW, by Miyoshi Kasei under the name UFTR, by Tomen under the name ITS and by titanium dioxide under the name Tioveil AQ.

The uncoated zinc oxide pigments are, for example:

Those sold under the name Z-Cote by Weijie technologies (Sunsmart),

those sold under the name Nanox by Haimassi company (Elementis),

those sold by the nano-top technology company (Nanophase Technologies) under the name Nanogard WCD 2025.

The zinc oxide pigments coated are, for example:

those sold under the name Zinc oxide CS-5 by Toshibi (Toshibi) (ZnO coated with polymethylhydrosiloxane),

those sold under the name Nanogard Zinc Oxide FN by the company nanotechnology top (as in Finsolv TN, benzoic acid C ₁₂ -C ₁₅ 40% dispersion in alkyl ester),

those sold under the names Daitopterion ZN-30 and Daitopterion ZN-50 by Daitong corporation (Daito) of Japan (dispersion in cyclomethicone/oxyethylenated dimethicone, containing 30% or 50% of nano zinc oxide coated with silica and polymethylhydrosiloxane),

those sold under the name NFD Ultrafine ZnO by Daikin (Daikin) (ZnO coated with a copolymer of perfluoroalkyl phosphate and based on perfluoroalkyl ethyl, as a dispersion in cyclopentasiloxane),

those sold under the name SPD-Z1 by the company Xinyue (Shin-Etsu) (ZnO coated with a silicone grafted acrylic polymer, dispersed in cyclomethicone),

Those sold under the name Escalol Z100 by ISP company (alumina treated ZnO dispersed in ethylhexyl methoxycinnamate/PVP-hexadecene/polymethylsiloxane copolymer mixture),

those sold under the name Fuji ZnO-SMS-10 by the company Fuji Pigment (ZnO coated with silica and polymethylsilsesquioxane),

those sold under the name Nanox Gel TN by Haimaos (benzoic acid C dispersed at a concentration of 55% in a polycondensate with hydroxystearic acid) ₁₂ -C ₁₅ ZnO in alkyl esters).

The uncoated cerium oxide pigment was prepared by the company Rona-PlanckSold under the name Colloidal Cerium Oxide.

Uncoated Iron oxide pigments are sold, for example, by the Arnaud company (Arnaud) under the names Nanogard WCD 2002 (FE 45B), nanogard Iron FE 45BL AQ, nanogard FE 45R AQ and Nanogard WCD 2006 (FE 45R) or by Mitsubishi company (Mitsubishi) under the name TY-220.

The coated iron oxide pigment is sold, for example, by the Arnold company under the name Nanogard WCD 2008 (FE 45B FN), nanogard WCD 2009 (FE 45B 556), nanogard FE 45BL 345 and Nanogard FE 45BL, or by the Basoff company under the name Transparent Iron Oxide.

Mention may also be made of mixtures of metal oxides, in particular titanium dioxide and cerium oxide, including mixtures of equal weights of titanium dioxide and cerium oxide coated with silicon dioxide, sold by the pool company under the name Sunveil A, and also mixtures of titanium dioxide and zinc dioxide coated with aluminum oxide, silicon dioxide and silicone, such as product M261 sold by the company Kevlar, or products M211 coated with aluminum oxide, silicon dioxide and glycerol, such as those sold by the company Kevlar.

The inorganic masking agent may be present in the composition according to the invention in a concentration of between 0.1% and 25% by weight and preferably between 0.2% and 10% by weight relative to the total weight of the composition.

Photoactive agents

According to a preferred embodiment of the present invention, the composition may comprise one or more photoactive agents.

The term "photoactive agent" thus means an agent that is chemically and/or physically unstable when exposed to UV radiation. The term "chemical instability" refers in particular to the degradation of the active ingredient, which may lead to, for example, a color change of the composition and/or a reduction of its activity. The term "physical instability" refers in particular to crystallization or precipitation of the active agent.

Photoactive agents according to the present invention may be selected from:

-a vitamin and a derivative thereof,

retinoic acid and its derivatives, in particular retinol and retinyl palmitate, benzene-1, 4-bis (3-methylene-10-camphorsulfonic acid), and n- (C4-C16) acyl-5-salicylic acid such as n-octanoyl-5-salicylic acid,

polyphenols of natural or synthetic origin, derivatives thereof, and plant extracts comprising the same,

-and mixtures thereof.

Vitamins, in particular ascorbic acid (vitamin C) and its derivatives, in particular its phosphate derivatives such as potassium salts of di-alpha-tocopherol di-ascorbyl phosphate (sold by kluyhou pharmaceutical corporation (Senju Pharmaceutical) under the index Sepivital EPC), magnesium ascorbyl phosphate and sodium ascorbyl phosphate (sold by Roche corporation (Roche) under the index stage-C50), and esters thereof such as ascorbyl acetate, palmitate and propionate; retinol (vitamin a) and its derivatives, especially its esters such as retinol acetate, palmitate and propionate; pantothenic acid (vitamin B) and its derivatives such as pantolactone, D-panthenol; biotin (vitamin H).

For the purposes of the present invention, the term "polyphenol derivative" refers in particular to polyphenol esters, glucosides and phosphates.

Among polyphenols, mention may be made mainly of phenolic acids and their derivatives (chlorogenic acids), and flavonoids, which represent a major subgroup of polyphenols.

Among the flavonoids, mention may be made in particular of chalcones, hydroxylated chalcones and derivatives thereof, such as phloretin, neohesperidin, phlorizin and aspartame (aspalathin); flavanones, such as hesperetin and naringin; flavonols such as quercetin and rutin; flavanols such as catechin and EGCG; flavones such as apigenin; anthocyanin.

Tannins, such as, inter alia, ellagitannins, can also be mentioned.

The polyphenols may be derived inter alia from plant extracts selected from green tea, apple, hops, guava or cocoa extracts, or from wood such as chestnut, oak, horse chestnut or hazelnut, extracts derived from rock tea or pomegranate extracts, japanese giant knotweed (Fallopia japonica, also known as Polygonum cupistadum or reynoutria japonica) extracts, grape extracts (e.g. those from grape species vinis vinifera), blackberry extracts, wine, peanut extracts and extracts from the following plant families: vitaceae, myrtaceae, dryopteridaceae, cyperaceae, gnetaceae, leguminosae, pinaceae, polygonaceae, moraceae, fagaceae, liliaceae, etc.

The polyphenols are especially baicalin, apigenin, leontopodic acid (leontopodic acid), ferulic acid, ellagic acid, resveratrol, myricetin and dihydroquercetin.

Preferred photoactive agents are selected from resveratrol, retinol, baicalin and vitamin C, and mixtures thereof, and preferably resveratrol.

The photosensitive and/or oxidation-sensitive active agent may be present in the composition according to the invention in a concentration ranging from 0.001% to 15% by weight, preferably from 0.01% to 10% by weight, and more particularly from 0.1% to 5% by weight, relative to the total weight of the composition.

The composition of the present invention may comprise an aqueous phase.

The term "aqueous phase" means a medium that is liquid at room temperature and atmospheric pressure and contains a substantial proportion of water relative to the total weight of the medium. The mass content of water in the aqueous composition is preferably greater than or equal to 10%, advantageously greater than or equal to 30%, preferably greater than or equal to 40%, or even greater than 50% by weight or greater than 80% by weight relative to the total weight of the composition.

The composition may be single phase or multi-phase.

The composition according to the invention may also contain at least one polar organic solvent, which is preferably physiologically acceptable.

The polar organic solvent is typically miscible with water.

As polar organic solvents, mention may be made of C ₁ -C ₆ A monoalcohol such as ethanol or isopropanol; c (C) ₁ -C ₆ Polyhydric alcohols such as glycerol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol and 1, 6-hexanediol; c (C) ₁ -C ₆ Alkylene glycols, such as ethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, pentylene glycol, and hexylene glycol; and mixtures thereof.

C in the composition of the invention ₁ -C ₆ The total content of alcohols is preferably from 0.1 to 10% by weight, and preferably from 1 to 5% by weight of C, relative to the total weight of the composition ₁ -C ₆ An alcohol.

C in the composition of the invention ₁ -C ₆ Of alkylene glycolsThe total content is preferably from 0.1 to 30% by weight, and preferably from 5 to 25% by weight of C relative to the total weight of the composition ₁ -C ₆ An alkylene glycol.

The composition according to the invention may be transparent or translucent and be coloured or uncoloured. The composition according to the invention may be free of pigments or dyes. Coloring may correspond to the addition of additional colorants.

The composition according to the invention may comprise a volatile solvent.

For the purposes of the present invention, the term "volatile solvent" means any liquid capable of evaporating upon contact with keratin materials at room temperature and atmospheric pressure.

The composition according to the invention may in particular be chosen such that the composition contains at least 5%, or even at least 30%, or even at least 40% of volatile solvents.

Fatty phase

The composition according to the invention may comprise a fatty phase. The fatty phase comprises one or more solid fatty substances, liquid fatty substances such as oils, or pasty fatty substances.

The composition may comprise oils, such as synthetic esters and ethers, linear or branched hydrocarbons of mineral or synthetic origin, fatty alcohols containing from 8 to 26 carbon atoms, partially hydrocarbon-based and/or silicone-based fluoro oils, silicone oils such as volatile or non-volatile Polymethylsiloxanes (PDMS) with linear or cyclic silicone chains, liquid or pasty at room temperature, and mixtures thereof, other examples being given below.

Thus, the composition according to the invention may comprise at least one volatile oil.

Volatile oil

For the purposes of the present invention, the term "volatile oil" means an oil (or non-aqueous medium) that can evaporate in less than one hour upon contact with the skin at room temperature and atmospheric pressure.

Volatile oils are volatile cosmetic oils which are liquid at room temperature, especially with non-zero at room temperature and atmospheric pressure In particular having a vapor pressure in the range from 0.13Pa to 40 000Pa (10 ^-3 To 300 mmHg), particularly ranging from 1.3Pa to 13 000Pa (0.01 to 100 mmHg), and more particularly ranging from 1.3Pa to 1300Pa (0.01 to 10 mmHg).

The volatile hydrocarbon-based oil may be chosen from hydrocarbon-based oils of animal or vegetable origin containing from 8 to 16 carbon atoms, and in particular branched C ₈ -C ₁₆ Alkanes (also known as isoparaffins), e.g. isododecane (also known as 2,4, 6-pentamethylheptane), isodecane, isohexadecane, and for example under the trade nameOr->And (3) oil sold.

Volatile oils which may also be used include volatile silicones, such as volatile linear or cyclic silicone oils, especially those having a viscosity of 8 centistokes (8X 10) ^-6 m ² S) and especially those containing from 2 to 10 silicon atoms and in particular from 2 to 7 silicon atoms, these silicones optionally comprising alkyl or alkoxy groups containing from 1 to 10 carbon atoms. As volatile silicone oils which can be used in the present invention, mention may be made in particular of polydimethylsiloxanes, octamethyltetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane, hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane and dodecamethylpentasiloxane having a viscosity of 5 and 6cSt, and mixtures thereof.

Volatile fluoro oils such as nonafluoromethoxybutane or perfluoromethyl cyclopentane, and mixtures thereof, may also be used.

It is also possible to use mixtures of the oils mentioned above.

Nonvolatile oil

The composition according to the invention may comprise a non-volatile oil.

For the purposes of the present invention, the term "non-volatile oil" means an oil having a vapor pressure of less than 0.13Pa, and in particular an oil having a high molar mass.

The non-volatile oil may be chosen in particular from hydrocarbon-based oils and/or silicone oils which may be fluorinated.

As non-volatile hydrocarbon-based oils which may be suitable for use in the present invention, mention may be made in particular of:

-a hydrocarbon-based oil of animal origin,

hydrocarbon-based oils of vegetable origin, such as plant sterol esters (phytostearyl ester), such as plant sterol oleate, plant sterol isostearate and lauroyl/octyldodecyl/plant sterol glutamate, for example triglycerides consisting of fatty acid esters of glycerol, sold under the name Eldew PS203 by Weisu company (Ajinomoto), the fatty acids of which may have a range C ₄ To C ₂₄ The chains may be linear or branched and saturated or unsaturated; these oils are in particular heptanoic or caprylic triglyceride, wheat germ oil, sunflower oil, grape seed oil, sesame oil, corn oil, apricot oil, castor oil, shea butter, avocado oil, olive oil, soybean oil, sweet almond oil, palm oil, rapeseed oil, cottonseed oil, hazelnut oil, macadamia nut oil, jojoba oil, alfalfa oil, poppy oil, pumpkin oil, blackcurrant oil, evening primrose oil, millet oil, barley oil, quinoa oil, rye oil, safflower oil, candelaeagnus oil, passion fruit oil or musk rose oil; butter wood fruit fat; or alternatively caprylic/capric triglyceride, such as those sold by DiBostirling (Steearinerie Dubois) or by Dinarminobell (Dynamit Nobel) under the name Miglyol And->Those that are sold are offered for sale,

hydrocarbon-based oils of mineral or synthetic origin, such as:

synthetic ethers containing from 10 to 40 carbon atoms;

straight-chain hydrocarbons or branched hydrocarbons of mineral or synthetic origin, such as petrolatum, polydecene, hydrogenated polyisobutenes, such as parleam, and squalane, and mixtures thereof, and in particular hydrogenated polyisobutene;

synthetic esters, of formula R ₁ COOR ₂ Wherein R is ₁ Represents a linear or branched fatty acid residue comprising from 1 to 40 carbon atoms, and R ₂ Represents in particular branched hydrocarbon-based chains containing from 1 to 40 carbon atoms, with the proviso that R ₁ +R ₂ Is more than or equal to 10.

The esters may be chosen in particular from among fatty acid esters, for example:

cetylstearyl octanoate, isopropyl esters, such as isopropyl myristate, isopropyl palmitate, ethyl palmitate, 2-ethylhexyl palmitate, isopropyl stearate, isopropyl isostearate, isostearyl isostearate, octyl stearate, hydroxylated esters, such as isostearyl lactate, octyl hydroxystearate, diisopropyl adipate, heptanoate, and in particular isostearyl heptanoate, alcohol or polyol octanoate, decanoate or ricinoleate, such as propylene glycol dioctanoate, cetyl octanoate, tridecyl octanoate, 2-ethylhexyl 4-diheptanoate, 2-ethylhexyl palmitate, alkyl benzoate, polyethylene glycol diheptanoate, propylene glycol 2-diethyl hexanoate, C12-C15 alcohol benzoates, hexyl laurate, pivalates, such as isotridecyl pivalate, isostearyl pivalate, octyl pivalate, isononanoyl isononanoate, isotridecyl nonanoate, hydroxylstearyl, and isostearyl lactate, such as isostearyl laurate;

Polyol esters and pentaerythritol esters, such as dipentaerythritol tetrahydroxy stearate/tetraisostearate;

esters of diol dimer and diacid dimer, such as Lusplan sold by japan refinement (Nippon Fine Chemical) and described in patent application FR 0302809Lusplan

Fatty alcohols which are liquid at room temperature and have branched and/or unsaturated carbon-based chains containing from 12 to 26 carbon atoms, such as 2-octyldodecanol, isostearyl alcohol, oleyl alcohol, 2-hexyldecanol, 2-butyloctanol and 2-undecylpentadecanol;

higher fatty acids such as oleic acid, linoleic acid and linolenic acid, and mixtures thereof; and

dialkyl carbonates, the two alkyl chains may be identical or different, e.g. Cetiol, from Corning CorpDioctyl carbonate sold;

nonvolatile silicone oils, such as nonvolatile Polydimethylsiloxane (PDMS), polydimethylsiloxanes containing alkyl or alkoxy groups in the side chains and/or at the ends of the silicone chains, each of these groups containing from 2 to 24 carbon atoms, phenylsilicones, such as phenylpolydimethylsiloxane, phenyltrimethylsiloxydiphenylsiloxane, diphenylpolydimethylsiloxane, diphenylmethyldiphenyltrisiloxane and 2-phenylethyltrimethylsiloxysilicate, and polydimethylsiloxane or phenylpolytrimethylsiloxane (viscosity less than or equal to 100 cSt), and mixtures thereof;

-and mixtures thereof.

Additive agent

The composition according to the invention may comprise at least one additive selected from adjuvants common in the cosmetic field, such as fillers, colorants, hydrophilic or lipophilic gelling agents, water-soluble or fat-soluble active agents, preservatives, humectants such as polyols and in particular glycerol, chelating agents, antioxidants, solvents, fragrances, odorants, pH regulators (acids or bases) and mixtures thereof.

The composition may contain at least one active agent having complementary activity in the field of solar protection, such as antioxidants, bleaching agents in an anti-pigmentation and de-pigmenting context, and anti-ageing active agents.

The additives may be selected from those mentioned in CTFA Cosmetic Ingredient Handbook [ CTFA cosmetic raw materials handbook ] 10 th edition (2004), of the institute of cosmetics and fragrances, washington, inc (Cosmetic and Fragrance Assn, inc.).

According to a specific embodiment, the composition according to the invention has a viscosity ranging from 20mpa.s (superfluid formulation) to 100mpa.s (creamy formulation), or even up to 10pa.s (viscous formulation), measured at 25 ℃ using a rotor 1, 2, 3 or 4 (depending on the viscosity range) for a Rheomat 180 machine at 200s ^-1 Performed by a method of manufacturing the same.

Presentation form

The composition according to the invention may be a lotion, two-phase composition, cream, emulsion, ointment or gel for skin, lips, hair or nails.

The term "physiologically acceptable medium" means a non-toxic medium that can be applied to keratin materials, in particular the skin, mucous membranes or the integuments.

The medium is adapted to the nature of the support to which the composition is to be applied and also to the form in which the composition is intended to be packaged.

The composition may be packaged in any packaging device, in particular made of thermoplastic material, or on any support intended for this purpose.

The packaging device may be a bottle, optionally with a dropper, a pump-action bottle, a spray bottle, a tube, a pouch, a can, or a wipe.

Cosmetic non-therapeutic photoprotection method

The photoprotective cosmetic composition may be applied by hand or using an applicator.

Application may also be carried out by spraying or jetting, for example using a piezoelectric or spraying device, or by a layer of the composition deposited on an intermediate support prior to transfer.

Examples

Examples of preparing polymers a):

molecular weight was determined by Gel Permeation Chromatography (GPC):

Samples were prepared by preparing a solution of the polymer at 10mg/ml in tetrahydrofuran. The sample was placed in an oven at 54 ℃ for 10 minutes and then in an oscillating shaker for 60 minutes to aid in dissolution. After visual inspection, the sample appeared to be completely dissolved in the solvent.

The prepared samples were analyzed using two polypore 300×7.5mm columns (manufactured by agilent technologies (Agilent Technologies)), a Waters 2695 chromatographic system, tetrahydrofuran mobile phase, and by refractive index detection. The sample was filtered through a 0.45 μm nylon filter before being injected into the liquid chromatograph. The standard used for calibration was an Easi visual narrow Polystyrene (PS) standard from agilent technologies.

Calibration was performed using polystyrene standards ranging from 2 520 000 to 162 daltons.

The system is equipped with a PSS secsecurity 1260 RI detector. The average molecular weight was determined using a polystyrene calibration curve. Chart recordings and determination of various molecular weights were made by the Win GPC Unichrom 81 program.

Melting point was determined by differential scanning calorimetry (or DSC):

this method describes a general procedure for determining the melting point of a polymer by differential scanning calorimetry. The method is based on the standards ASTM E791 and ASTM D34182, and the DSC calibration is performed according to the standard ASTM E9672.

Behenyl acrylate/2-hydroxyethyl acrylate copolymer (polymer 1):

in a 4-necked flask equipped with a side-blade mixer, an internal thermometer, two funnels, a reflux condenser and an extension for the other two necks, after oxygen has been removed from the system by nitrogen flushing for 20 minutes, 175g of behenyl acrylate, 25g of 2-hydroxyethyl acrylate and 0.4g of 2,2' -azobis (2-methylbutyronitrile) (Akzo Nobel) were added to 40g of isopropanol with stirring during 60 minutes at 80 ℃. The mixture was stirred at 80℃for 3 hours. The solvent was then removed by vacuum distillation, then 1g dilauroyl peroxide was added and the reaction was continued at 110 ℃ for 60 minutes. Repeating the steps. The mixture was then cooled to 90 ℃, a demineralized water stream was added and the mixture was then stirred. The water was removed by vacuum distillation.

Molecular weight: mn=7300 g/mol, mw=21,000, mw/mn=2.8

Melting point: 65 DEG C

Examples 1 to 3

For each composition, viscosity was measured at different temperatures and/or stability over time was studied and/or sensory aspects were evaluated during and after application to the skin.

Viscosity measurement

Typically at 25℃for 200s ^-1 Rheomat equipped with a rotor adapted to the viscosity range and mainly rotor No. 3 is used at the shear rate of (a)The viscometer measures the viscosity after the rotor rotates in the composition for 10 minutes (after which stabilization of the viscosity and the rotational speed of the rotor is observed).

Investigation of stability over time at different temperatures

Stability over time was studied by observing the composition with respect to its macroscopic appearance, its microscopic appearance, and changes in viscosity and pH at different temperatures (e.g., room Temperature (RT), 4 ℃ or 45 ℃).

Protocol for evaluation of tack, shine and greasiness

The tacky, shiny and greasy effect of the compositions was evaluated by the sensory panel.

Each composition was added at 2mg/cm ² Is applied to the forearm. The product is applied by a circular motion until it has penetrated (about 30 seconds). After 2 minutes of drying, the tack, shine and greasiness effects were evaluated by placing the back of the hand on the treated area, on a scale ranging from 1 to 15, with 1 being considered a less tacky or less shiny or less greasy reference and 15 being considered a very tacky or very shiny or very greasy reference.

In the following table, SM means starting material and AM means active material.

The following O/W emulsions were prepared:

preparation method

The starting materials were first carefully weighed out using a balance (precision = 0.01 g).

Compositions 1 to 3 were prepared according to the following procedure:

the fatty phase a and polymer B were heated at 70 ℃ until the polymer was completely melted and dissolved.

In a further vessel, dispersed in an aqueous phase C, which contains in particular a hydrophilic gel polymer, and neutralized with a base, the entire phase is then heated to 70 ℃.

The oil phase (at 70 ℃) is incorporated into the aqueous phase (at 70 ℃) with vigorous stirring (rotor/stator type), and the emulsion thus obtained is cooled to 25 ℃.

Phase D was incorporated with stirring (rotor/stator type) until a smooth homogeneous mass was obtained.

The composition according to the invention is stable. It has significantly reduced shine, tacky effect and greasy appearance compared to those of the comparative composition.

Example 4:

the following O/W emulsions were prepared:

in vitro SPF

According to B.L. Diffey J.Soc.Cosmet.chem. [ society of cosmetic chemists ]]The "in vitro" method described in 40, 127-133 (1989) determines the Sun Protection Factor (SPF). Measurements were made by a UV-2000S spectrophotometer from blue phenanthrene optics (Labsphere). Each composition was in the form of a homogeneous and even deposit at 1.3mg/cm ² Is applied to thick PMMA plates.

The composition is stable at 4 ℃, 25 ℃ and 45 ℃ for 2 months.

It has an in vitro SPF of 26.6.+ -. 0.5 and a PPD UVA index of 10.5.+ -. 0.2.

The greasy appearance and tackiness was evaluated by a sensory panel consisting of 10 individuals. After application to the skin, the composition was neither tacky (grade 2.5) nor greasy (grade 2.5).

Examples 5 to 7

The following composition was prepared:

the manufacturing method comprises the following steps:

aqueous phase a was prepared by heating to 75 ℃ and placed in a deflocculating centrifuge at 450 rpm.

Then, xanthan gum and nicotinamide are added and stirred until the composition is homogeneous. Then, A2, copolymer and base are added.

Resveratrol and isopropyl lauroyl sarcosinate B1 were heated to 40 ℃.

Phase B was heated to 75 ℃ with magnetic stirring. Just prior to emulsification, B1 was added to B. Emulsification was carried out by adding hot fat phase B to the aqueous phase while vigorously stirring using a Moritz mixer. Rest for 5 minutes while lowering the temperature (nominal value set to 25 ℃). Below 43 ℃, stirring was started using a deflocculating centrifuge and phase C (ammonium acryloyldimethyl taurate/VP copolymer) was added and cooling continued to 25 ℃.

The remaining ingredients D, E and F were added at 30 ℃.

Then, ethanol was added at 25 ℃ and pH was adjusted with lactic acid H.

The composition according to the invention is compared with a composition comprising another polymer (example 6) or a surfactant system (example 7).

Composition 5 according to the invention is fine, smooth, homogeneous and glossy. Which does not show any crystallization under polarized light. It is stable over time (2 months of storage at 45 ℃).

At T0, compositions 6 and 7 are incompatible, they show oil release.

Composition 5 has excellent bioavailability of resveratrol.

Claims

1. A composition, in particular a cosmetic composition, comprising at least:

-a) one or more polymers comprising monomer units of formulae (a) and (B):

wherein:

r1 is in each case independently selected from alkyl and alkenyl,

and is also provided with

At least 60% by weight of the radicals R1 being behenyl radicals, the weight percentages being relative to the sum of all the radicals RI present in the polymer,

and is also provided with

The weight ratio of the sum of all hydroxyethyl acrylate units to the sum of all acrylate units carrying the group R1 ranges from 1:30 to 1:1;

And the sum of the total units A and B is at least 95% by weight with respect to the total weight of the polymer,

the polymer having a number average molecular weight Mn ranging from 2000 to 9000g/mol,

-b) one or more UV screening agents, and

-c) one or more copolymers of acrylamido-2-methylpropanesulfonic acid with one or more nonionic monomers.

2. Composition according to the preceding claim, in which in polymer a) R1 consists of an alkyl group, preferably a C16-C22 alkyl group, and more preferably a behenyl group.

3. Composition according to any one of the preceding claims, wherein in polymer a) at least 70% by weight, preferably at least 80% by weight, more preferably at least 90% by weight of the radicals R1 are behenyl radicals.

4. Composition according to any one of the preceding claims, in which, in polymer a), all the radicals R1 are behenyl radicals.

5. Composition according to any one of the preceding claims, in which the weight ratio of the sum of all hydroxyethyl acrylate units to the sum of all acrylate units bearing the group R1 in polymer a) ranges from 1:15 to 1:1, and preferably ranges from 1:10 to 1:4.

6. The composition according to any of the preceding claims, wherein polymer a) has a number average molecular weight Mn ranging from 5000 to 9000 g/mol.

7. Composition according to any one of the preceding claims, wherein the lipophilic polymer has a melting point ranging from 60 ℃ to 69 ℃ and preferably ranging from 63 ℃ to 67 ℃.

8. Composition according to any one of the preceding claims, in which the content of polymer a) is from 0.01% to 10% by weight relative to the total weight of the composition.

9. The composition of any of claims 1 to 8, wherein the UV-screening agent is selected from soluble or insoluble organic UV-screening agents, mineral UV-screening agents, and mixtures thereof.

10. The composition according to any one of claims 1 to 9, wherein the content of UV screening agent is 0.01% to 60% by weight relative to the total weight of the composition.

11. The composition of any one of claims 1 to 10, wherein the copolymer c) comprises one or more nonionic monomers selected from water-soluble ethylenically unsaturated monomers, hydrophobic monomers, or mixtures thereof.

12. Composition according to any one of the preceding claims, wherein the copolymer c) comprises one or more nonionic monomers selected from the following nonionic water-soluble monomers:

A (meth) acrylamide which is a compound of formula (I),

n-vinylacetamide and N-methyl-N-vinylacetamide,

n-vinylformamide and N-methyl-N-vinylformamide,

-maleic anhydride and the like,

the reaction of the vinyl amine with the catalyst,

-CH ₂ Vinyl alcohol of the type CHOH,

-a water-soluble vinyl monomer of formula (B):

wherein:

-R ₁₅ selected from H, -CH ₃ 、-C ₂ H ₅ and-C ₃ H ₇ ；

-X ₂ Selected from:

13. The composition according to any of the preceding claims, wherein the copolymer c) comprises one or more nonionic monomers selected from the following nonionic hydrophobic monomers:

-CH ₂ ＝CH-OCOCH ₃ Vinyl acetate of (a);

The presence of acrylonitrile in the mixture of the polymer and the catalyst,

-caprolactone;

vinyl chloride and vinylidene chloride;

-a hydrophobic vinyl monomer of formula (C):

wherein:

-X ₃ selected from:

--OR ₂₄ alkyl oxides of the type wherein R ₂₄ A linear or branched, saturated or unsaturated hydrocarbon-based group containing from 1 to 6 carbon atoms;

-a vinyl monomer of formula (D):

14. Composition according to any one of the preceding claims, in which the copolymer c) is chosen from:

copolymers of acrylamide-2-methylpropanesulfonic acid ammonium with vinylpyrrolidone,

AMPS/cetostearyl methacrylate copolymer ethoxylated with 25mol of ethylene oxide.

15. Composition according to any one of the preceding claims, in which the copolymer c) is present in the composition according to the invention in an amount ranging from 0.1% to l0%, preferably from 0.2% to 8% by weight and more preferably from 0.5% to 5% by weight relative to the total weight of the composition.

16. The composition of any of the preceding claims, wherein the composition further comprises one or more photoactive agents.

17. Composition according to the preceding claim, in which the photoactive agent is chosen from:

-a vitamin and a derivative thereof,

-and mixtures thereof.

18. Composition according to the preceding claim, wherein the photoactive agent is selected from resveratrol, retinol, baicalin and vitamin C, and mixtures thereof, and preferably resveratrol.

19. Composition according to any one of claims 17 and 18, wherein the photoactive agent is present in a concentration ranging from 0.001% to 15% by weight, preferably from 0.01% to 10% and more particularly from 0.1% to 5% relative to the total weight of the composition.

20. A non-therapeutic method for photoprotection of keratin materials against solar UV radiation, comprising the step of applying to the keratin materials a composition according to claims l to 19.

21. A non-therapeutic cosmetic method for limiting skin darkening and/or improving the color and/or uniformity of skin tone, the method comprising the step of applying to the skin a composition according to claims 1 to 19.

22. A non-therapeutic cosmetic method for preventing and/or treating signs of ageing of keratin materials, comprising the step of applying to the surface of the keratin materials a composition according to claims 1 to 19.